KR20090049681A - Low temperature process for preparation of polyimide - Google Patents

Abstract

The present invention is a method for producing a polyimide resin by imidating a polyamic acid under a specific diamine compound catalyst, the reaction is smoothly performed not only at a high temperature of 200 ° C or more but also at a low temperature of 200 ° C or less. It is related with the method of manufacturing the high quality polyimide resin which significantly reduces the amount of catalyst which remains in a polyimide, and a molecular weight fall phenomenon does not occur.

Polyamic acid, polyimide, low temperature, catalyst, diamine

Description

Low temperature process for preparation of polyimide

The present invention is a method for producing a polyimide resin by imidating a polyamic acid under a specific diamine compound catalyst, the reaction is smoothly performed not only at a high temperature of 200 ° C or more but also at a low temperature of 200 ° C or less. It is related with the method of manufacturing the high quality polyimide resin which significantly reduces the amount of catalyst which remains in a polyimide, and a molecular weight fall phenomenon does not occur.

Polyimide resins are super engineering plastics useful for applications in electrical, electronic components and other high heat resistant polymers. They exhibit excellent heat resistance, mechanical properties, electrical properties, thermal expandability, processability, optical properties, and the like, and include circuit boards, substrates for copper clad laminates, electrical insulation protective films, insulation films for multilayer circuits, and alignment films of liquid crystal display devices. And it is widely used in the field of electronic components and the field of polymer materials capable of meeting the desired performance in various components requiring high heat resistance of 300 ℃ or more.

Generally, such a polyimide is prepared by using a polyamic acid obtained by condensing tetracarboxylic dianhydride and diamine as an amide group linkage in a solvent as a precursor, followed by heat dehydration to form an imide ring, or chemical dehydration using a dehydrating agent. By dehydration and cyclization.

In general, polyimide has a very high glass transition temperature of 350 ° C. or higher, and therefore, once polyimide is formed from polyamic acid by imidization, it is difficult to be formed by heating above the glass transition temperature. Since the physical properties are lowered by the resin, the resin is obtained in the necessary properties such as a film when forming a polyimide from the polyamic acid.

The process of dehydrating cyclization from polyamic acid by heating method generally requires a high temperature of 300 ° C. to 400 ° C., and it is difficult to mold after polyimide formation. Therefore, imidation is performed on a part material to form a polyimide thin film or film. Done. When producing a polyimide resin in a general film form, the limitation of the manufacturing temperature is limited to the energy consumption or the design of the manufacturing apparatus, but when the polyimide resin forming site is not suitable for a high temperature process, polyimide resin formation itself becomes difficult. . In particular, in the case of application as an interlayer insulating material and a coating material to an organic material electronic device component which is actively progressed in recent years, it is required to lower the formation temperature of polyimide to 200 degrees C or less.

In addition, methods of forming polyimides through dehydration cyclization by chemical methods using dehydrating agents enable the formation of polyimides at such low temperatures, but the use of more than one equivalent of dehydrating agent and the generation of more than equivalent equivalents of dehydration byproduct Physical deterioration of the polyimide resin formed by imidation which does not occur becomes large.

It has been known in the art to perform imidization by adding catalysts such as acids and bases with such dehydrating agents. As the acid catalyst, p - hydroxyphenyl acetic acid (p -hydroxyphenylacetic acid) using an organic acid, such as have been reported as measured by the polyimide by imidization proceeds at a low temperature of less than 200 ℃ [M. Oba, J. Polym. Science: Part A: Polymer Chemistry , 1996 , 34 , 651-658. In addition, studies of low temperature imidization conditions using a base catalyst have been conducted for reactions using amines. Generally, base catalysts include triethylamine, pyridine, 1,4-diazabicyclo [2.2.2] octane, (1 , 4-diazabicyclo [2.2.2] octane), 1,8-diazabicyclo [5.4.0] unde-7-cene (1,8-diazbicylco [5.4.0] undec-7-ene) Is being reported. However, when the basicity is low, such as triethylamine or pyridine, an equivalent or more is used, and at a temperature below 200 ° C., there is no effect of accelerating imidization.

In addition, high nucleophilic organic base such as 1,4-diazabicyclo [2.2.2] octane has been reported to show imidization effect at low temperature [M. Ueda, Chem . Lett . 2004 , 33 , 1156-1157. However, 1,4-diazabicyclo [2.2.2] octane is effective in promoting imidization, but when the thickness of polyimide resin becomes thicker to form a film with a thickness of 10 μm or more, most of the amine catalyst used is trapped in the resin. The problem remains. In addition, 1,4-diazabicyclo [2.2.2] octane and 1,8-diazabicyclo [5.4.0] ound-7-cene are polyamic as nucleotides with higher nucleophilicity than general alkyl amines. The action of promoting reverse reaction by mixing with acid to lower the molecular weight of polyamic acid has a big problem.

The present invention is capable of forming a polyimide resin from a polyamic acid by performing an imidization reaction at a low temperature of 200 ° C. or lower, and having a high imidation ratio, no additional compound remaining in the resin, and a poly-resistable material. It is intended to present a method of making a mead.

Thus, the imidization reaction is to be carried out in the presence of a specific catalyst, the catalyst can proceed the reaction by lowering the activation energy required in the formation of the imide ring in order to promote imidization at low temperature, the catalyst of the polyamic acid It does not show a problem of reducing the molecular weight by showing a reverse reaction, and selects and uses that does not remain after the production of the polyimide resin, resulting in a decrease in physical properties. As a result, the present invention provides a method for producing a polyimide capable of achieving a desired effect by carrying out the imidization reaction of a polyamic acid under a tertiary diamine compound catalyst having a suitable carbon skeleton between two amine groups.

The present invention is characterized by a catalyst for imidization reaction represented by the following formula (1).

In Chemical Formula 1, R ₁ , R ₂ , R ₃ , R <_4> , R <_5> and R <_6> represent a hydrogen atom, a C1-C12 alkyl group, or a C1-C12 hydroxy alkyl group, respectively, and n is an integer of 0-4. Preferably, R ₁ , R ₂ , R ₃ and R ₄ are each an alkyl group having 1 to 12 carbon atoms, and R ₅ and R ₆ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a hydrocarbon having 1 to 12 carbon atoms. Roxy alkyl group is represented and n is an integer of 0-4.

In addition, the present invention is a method for producing a polyimide resin by imidization of a polyamic acid, further another method for producing a polyimide resin using a diamine compound represented by the formula (1) as the catalyst for the imidization reaction There is this.

The present invention uses a specific diamine compound as a catalyst in the imidation reaction of polyamic acid, and enables the imidization reaction to be carried out not only at a high temperature but also at a significantly lower temperature than that of the prior art, specifically, 200 ° C or less. It is possible to obtain a high quality polyimide resin without remaining of the catalyst and without lowering the molecular weight of the polyamic acid, and its use is expected in various fields.

The present invention relates to a method for producing a polyimide by carrying out an imidation reaction of a polyamic acid under a specific trivalent diamine compound catalyst.

Specifically, in order to promote the imidization reaction at a low temperature of 200 ° C. or lower, instead of the conventional high temperature reaction, the present invention considers a compound capable of lowering the activation energy required to form an imide ring to allow the reaction to proceed. In one step, the nitrogen atom of the amide nucleophilically attacks the carbonyl carbon to form a ring, and in this intermediate, a cyclization mechanism is composed of two steps in which the hydrogen atom bonded to the nitrogen atom dissociates and dehydrates with water. The activation energy of each step is estimated. From this, the imidization of high temperature heating conditions confirmed that the second step of dissociating hydrogen atoms bound to nitrogen atoms and dehydrating them into water was a reaction rate determination step, and proposed an effective catalytic method of reducing activation energy of this step.

The application of the basic catalyst is effective in removing hydrogen atoms bound to nitrogen as protons, but the carboxyl groups included in the polyamic acid act as an acid functional group, which is expected to first react with the added amine to form ammonium salts. It is proposed to apply a diamine compound catalyst having two or more amine groups as a suitable catalyst for removing hydrogen atoms from nitrogen atoms in. The two amine groups should be able to be linked to a flexible carbon skeleton so that the other amine groups can act at the reaction site as a base even if one forms a carboxyl group and an ammonium salt.

In the conventional catalytic imidization method using amines, monoamines are mostly used, and diamines such as 1,4-diazabicyclo [2.2.2] octane are composed of a rigid skeleton having no flexibility, and thus hardly appear as a diamine.

That is, the present invention is not high nucleophilic but composed of diamine and due to the flexibility of the skeleton, the two amine groups effectively act at the reaction site of the imidization to promote dehydration cyclization at low temperature, thereby increasing the imidization rate of polyamic acid The present invention relates to a process for producing a polyimide by carrying out the imidation reaction of a polyamic acid under a specific catalyst.

Referring to the method for producing a polyimide according to the present invention in more detail as follows.

The polyamic acid used as a reaction raw material is generally used in the art and is not particularly limited. However, the polyamic acid is prepared through the reaction of tetracarboxylic dianhydride and diamine, and is generally preferred to obtain a polyimide having excellent heat resistance and mechanical properties. Preferably, aromatic acid dianhydrides and aromatic diamines are used.

The tetracarboxylic dianhydride is commonly used in the art, but is not particularly limited, and specifically, pyromelitc dianhydride, 1,2,3,4-benzene tetracarboxylic dianhydride, and benzophenone tetracarbide Carboxylic dianhydride, bis (dicarboxyphenylether) dianhydride, bis (dicarboxyphenylsulfone) dianhydride, bis (dicarboxyphenylsulfide) dianhydride, bis (dicarboxyphenyl) propane dianhydride, bis (dicarboxyphenyl Hexafluoropropane dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetra carboxylic dianhydride, fluorine-substituted derivatives and alkyl-substituted derivatives thereof and the like can be used alone or in combination of two or more thereof. Acid dianhydrides linked to the corresponding aliphatic carbon skeletons are generally used in the art, and specifically, may be used alone or in the form of a mixture of two or more cyclobutane tetracarboxylic dianhydrides.

As the diamine, aromatic and aliphatic diamines may be used, and specifically, p -phenylene diamine, m -phenylene diamine, diamino diphenyl ether, diamino diphenyl sulfone, diamino diphenyl sulfide, diamino benzophenone, bis (Aminophenyl) propane, bis (aminophenyl) hexafluoropropane, diamino biphenyl, diamino pyridine, diamino naphthalene, and fluorine substituted derivatives and alkyl substituted derivatives thereof, or mixtures of two or more thereof may be used.

The reaction of the acid dianhydride and diamine is carried out under a solvent capable of dissolving these reactants and the polyamic acid, which is the desired product. The solvent is generally not particularly limited in the art, but specifically N, N -dimethylformamide, N, N -dimethylacetamide, N -methyl-2-pyrrolidone, cresol, pyridine, dimethyl sulfoxide, γ -Butyrolactone or the like and a mixed solvent thereof can be used.

These solvents are selected so as to maintain the concentration in the range of 1 to 40% by weight, and used to select the temperature and concentration to control the molecular weight of the polyamic acid formed. At this time, the reaction temperature is generally carried out in the art, but is not particularly limited, but is carried out in the range of -20 ℃ to 100 ℃.

The prepared polyamic acid may be used as a solvent or a polyamic acid solution containing a solvent.

Next, a polyimide resin is prepared by performing an imidization reaction of the polyamic acid prepared above. In general, a polyamic acid solution is applied on a support and subjected to imidization to perform a casting method of obtaining a polyamide resin in the form of a film. This casting method is an example, and the present invention is not limited to this casting method.

At this time, the support is generally used in the art, there is no limitation depending on the desired form and parts, and also the thickness of the film to be formed is not limited, but it is preferable to keep the range of 100 nm to 500 μm specifically. When the thickness is less than 100 nm, it is difficult to act as a thin film, and when it exceeds 500 µm, it is preferable to maintain the above range because problems occur in uniform film forming.

The present invention is characterized in that the technical configuration of the trihydric diamine compound represented by the following formula (1) under a catalyst so that the imidization proceeds sufficiently under the conditions of low temperature below 200 ℃ without high temperature heating as in the prior art have.

[Formula 1]

In Chemical Formula 1, R ₁ , R ₂ , R ₃ , R <_4> , R <_5> and R <_6> represent a hydrogen atom, a C1-C12 alkyl group, or a C1-C12 hydroxy alkyl group, respectively, and n is an integer of 0-4. Preferably, R ₁ , R ₂ , R ₃ and R ₄ are each an alkyl group having 1 to 12 carbon atoms, and R ₅ and R ₆ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a hydroxy having 1 to 12 carbon atoms. An alkyl group is represented and n is an integer of 0-4.

The catalyst is generally used in the art and is not particularly limited, but specifically N, N, N ', N' -tetramethylethylenediamine, N, N, N', N' -tetramethylpropylenediamine, and N , N, N ', N' -tetramethylbutylenediamine and the like can be used.

As described above, the diamine-based compound applied as a catalyst in the present invention is two amine groups connected by at least 2 carbon atoms and connected by a flexible carbon skeleton. The design and application of such amines is based on the use of diamines as an optimized structure that can promote the transfer of protons when completing the imide ring in the above-described intermediate. That is, one amine group in the diamine compound forms an ammonium salt with a carboxyl group, and the other amine group serves to remove hydrogen atoms in the nitrogen atom of the intermediate with protons to promote imidization reaction.

The effect of using the diamine catalyst is apparent when comparing the reactivity of N, N, N ', N' -tetramethylethylenediamine with triethylamine having a similar basicity, using 10% by weight of N, N, N ', N' -tetramethylethylenediamine forms a polyimide resin with the imidation ratio of 100% on the conditions passed for 30 minutes at 200 degreeC. On the other hand, triethylamine shows a 72% imidation level even when used in an excess amount of equivalent, thus confirming that there is little effect as a catalyst. That is, it can be seen that the coordination action of two spatially adjacent amine groups contributes to the effect of reaction promotion.

In addition, when the same diamines were connected with a rigid carbon skeleton such as N, N' -dimethylpiperazine, the diamine catalyst was not found to be active. This is because the two amine groups can be placed in the intermediate to act as a base. It is important to note that the two amine groups are linked by a flexible carbon backbone, which makes it important to work.

Among the diamine compounds of the present invention, in particular, N, N, N ', N' -tetramethylethylenediamine, N, N, N', N' -tetramethylpropylenediamine are each a liquid phase having a boiling point of 120 ° C and 145 ° C, respectively. This property as a catalyst shows a great advantage in completely removing the catalyst remaining in the film after polyimide resin formation. 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] unde-7-cene and the like, which have been suggested to be used as imidization catalysts in the past, have high boiling points of compound materials. Due to this, there is a problem that the residual amount increases in the film after forming the polyimide resin.

In addition, the diamine compound of the present invention performs a catalysis smoothly even in a state where the basicity and nucleophilicity are not high. Thus, 1,4-diabetes exhibiting high imidization efficiency at a relatively low temperature (specifically, 200 ° C.). Javaicyclo [2.2.2] octane and 1,8-diazabicyclo [5.4.0] unde-7-cene exhibit high nucleophilicity attributable to their structure, thus promoting the reverse reaction of polyamic acid. Will promote dissociation. This action lowers the molecular weight of the polyamic acid and acts as a problem in producing a polyimide resin having a desired molecular weight range.

In addition, since the amine catalyst is difficult to be added to and stored in the polyamic acid solution even in the actual manufacturing process, it causes a process problem that must be added and dissolved immediately upon application to the support of the polyamic acid solution in the manufacturing process.

The catalyst of the present invention is a relatively mild diamine compound and has the advantage of showing sufficient imidization efficiency with little degradation of the polyamic acid, and this characteristic is pre-added with the amine catalyst to the polyamic acid solution in the actual polyimide resin manufacturing process. It has the advantage that it can be used in the polyimide film manufacturing process while dissolving and storing.

Such a diamine catalyst can be used in the range of 1 to 200% by weight, preferably 1 to 100% by weight, more preferably 5 to 10% by weight, based on the polyamic acid solids. If the amount used is less than 1% by weight, the imidization reaction rate is remarkably low, and thus the effect as a catalyst is insignificant, and when used in excess of 200% by weight, there is no further improved effect, so it is not economical, thus maintaining the above range. It is preferable.

The imidization reaction can be performed in a low temperature range of 200 ° C. or lower as well as a conventional high temperature range of 200 ° C. or higher, and specifically, may be performed in a wide temperature range of 100 ° C. to 400 ° C. In other words, it is possible to produce a high-quality polyimide resin of interest even at a low temperature in the range of 100 ~ 200 ℃ where the reaction was not carried out conventionally, preferably at 160 ℃ or more to minimize the amount of residual solvent and catalyst Good for

If the reaction temperature is less than 100 ℃, the removal of water dehydrated in the reaction is not smooth, such as the formation of fine pores in the film is deteriorated, and if it exceeds 400 ℃, the oxidation and decomposition of the polyimide resin begins to appear. Therefore, it is preferable to maintain the above range because the physical properties of the resin may be reduced.

This temperature is carried out at room temperature to be heated step by step to improve the physical properties of the produced polyimide resin bar, for example, in the case of the casting method by applying a polyamic acid dissolved in the diamine compound according to the present invention on a support It is preferable to prepare a polyimide resin by heating at about 60 ° C. for 30 minutes, at about 100 ° C. for 30 minutes, and at 200 ° C., and heating stepwise for 30 minutes and the like.

When the imidation reaction is carried out using a specific diamine compound according to the present invention as a reaction catalyst, the imidation ratio is 95 to 100%, and the amount of residual catalyst in the polyimide resin is 0 to 10% by weight.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.

Example 1

30 g of 4,4'-oxydianiline was added to the reactor, and 564 g of dimethylacetamide was added thereto and stirred. Thereafter, the reactor temperature was set at 0 ° C., and 32.7 g of pyromellitic dianhydride was added and stirred for 1 hour to react. Next, the reaction mixture was heated to room temperature for 4 hours to prepare a polyamic acid solution.

To the polyamic acid solution prepared above, 5% by weight of N, N- dimethylacetamide was diluted with respect to the polyamic acid solution, and 6 g of N, N, N ', N' -tetramethylethylenediamine (polyamic acid solid content). 10 wt%), and stirred for 10 minutes. The solution prepared above was then applied on a glass support with a film applicator to a thickness of 700 μm and placed in a heating oven. Next, a polyimide resin was prepared by passing stepwise at 60 ° C. for 30 minutes, 100 ° C. for 30 minutes, and 200 ° C. for 30 minutes.

The prepared polyimide film was measured for imidization using IR, and the residual catalyst amount was confirmed by TGA-Mass (Thermo-gravimetric analysis-mass spectroscopy), and the results are shown in Table 1 below.

Example 2

A polyimide resin was prepared in the same manner as in Example 1, using 5 wt% of N, N, N ', N' -tetramethylethylenediamine based on the polyamic acid solids.

The prepared polyimide film was measured for imidization using IR, and the residual catalyst amount was confirmed by TGA-Mass (Thermo-gravimetric analysis-mass spectroscopy). The results are shown in Table 1 below.

Example 3

Example but 1 In the same manner as, N, N, N ', N' - tetramethylethylenediamine instead of the polyamic acid with respect to the solid content of N, N, N ', N ' in-tetramethyl propylene using the diamine 10% by weight To produce a polyimide resin.

The prepared polyimide film was measured for imidization using IR, and the residual catalyst amount was confirmed by TGA-Mass (Thermo-gravimetric analysis-mass spectroscopy). The results are shown in Table 1 below.

Comparative Example 1

In the same manner as in Example 1 , polyimide resin was prepared using 10% by weight of triethylamine based on polyamic acid solids instead of N, N, N ', N' -tetramethylethylenediamine.

The polyimide film prepared above was measured for imidization using IR, and the residual catalyst amount was confirmed by TGA-Mass (Thermo-gravimetric analysis-mass spectroscopy). The results are shown in Table 1 below.

Comparative Example 2

In the same manner as in Example 1 , polyimide resin was prepared using 100% by weight of triethylamine based on the polyamic acid solids instead of N, N, N ', N' -tetramethylethylenediamine.

The prepared polyimide film was measured for imidization using IR, and the residual catalyst amount was confirmed by TGA-Mass (Thermo-gravimetric analysis-mass spectroscopy), and the results are shown in Table 1 below.

Comparative Example 3

In the same manner as in Example 1 , polyimide resin was prepared using 10% by weight of 1,4-dimethylpiperazine based on polyamic acid solids instead of N, N, N ', N' -tetramethylethylenediamine. .

The prepared polyimide film was measured for imidization using IR, and the residual catalyst amount was confirmed by TGA-Mass (Thermo-gravimetric analysis-mass spectroscopy). The results are shown in Table 1 below.

Comparative Example 4

The same procedure as in Example 1 was carried out, except that 10 wt% of 1,4-diazabicyclo [2.2.2] octane was used based on the polyamic acid solid instead of N, N, N ', N' -tetramethylethylenediamine. To produce a polyimide resin.

The prepared polyimide film was measured for imidization using IR, and the residual catalyst amount was confirmed by TGA-Mass (Thermo-gravimetric analysis-mass spectroscopy). The results are shown in Table 1 below.

Comparative example  5

In the same manner as in Example 1, N, N, N ', N' -tetramethylethylenediamine was carried out under a catalyst-free condition to prepare a polyimide resin.

The prepared polyimide film was measured for imidization using IR, and the residual catalyst amount was confirmed by TGA-Mass (Thermo-gravimetric analysis-mass spectroscopy). The results are shown in Table 1 below.

division Catalyst type and amount used (wt% ¹⁾ ) Reaction temperature (℃) Imidization Rate (%) Residual Catalyst Amount (wt% ²⁾ ) Example 1 N, N, N'N' -tetramethylethylenediamine (10) 200 100 0 Example 2 N, N, N'N' -tetramethylethylenediamine (5) 200 96 0 Example 3 N, N, N'N' -tetramethylpropylenediamine (10) 200 95 0 Comparative Example 1 Triethylamine (10) 200 72 0 Comparative Example 2 Triethylamine (100) 200 80 0 Comparative Example 3 1,4-dimethylpiperazine (10) 200 81 7 Comparative Example 4 1,4-diazabicyclo [2,2,2] octane (10) 200 100 8 Comparative Example 5 - 200 70 - 1):% by weight of polyamic acid solids. 2):% by weight of residual catalyst contained in the total amount of polyimide produced

As shown in Table 1, the imidization reaction of the polyamic acid at a low temperature of 200 ° C. or lower using a specific trivalent diamine compound according to the present invention using a catalyst results in completion of the imidization ratio of 95% or more. It was confirmed that a polyimide resin in a state without a residual catalyst was produced.

Specifically, Examples 1, 2 and 3 can be seen that the diamine compound used as a catalyst is effective in the imidization of the two amine groups effectively connected by a flexible carbon skeleton of an appropriate distance. This diamine compound can clearly confirm the superiority of the effect as a catalyst when compared with the results of Comparative Examples 1 and 2 applying triethylamine showing similar properties of the amine base. In other words, in the imidization reaction using triethylamine, the effect of imidization improvement is very weak compared with the result of Comparative Example 5 without using a catalyst, and the degree of improvement is very good even in the result of Comparative Example 2, which greatly increased the amount of its use. You can see that it is low.

As a result, it can be confirmed that the diamine compound catalyst including two adjacent amine groups as in the present invention is very effective for the imidization reaction of polyamic acid.

In addition, in the diamine compound catalyst applied in the present invention, Example 1, in which two amine groups were connected by two carbon skeletons, showed slightly better results than Example 3, in which three carbon skeletons were used. It shows that regulation is important for effectively proceeding imidization. This effect is apparent in the results using the 1,4-dimethylpiperazine exemplified in Comparative Example 3. In other words, when the diamine compound but two amine groups are connected by a rigid carbon skeleton and do not function properly in the reaction intermediate, it can be seen that there is no effect as a diamine catalyst. Comparative Example 4 shows a result of having a problem that the catalyst residual amount is very high even when the imidization is completed because of its excellent function as a catalyst, which is not sufficiently vaporized in the low temperature imidization reaction conditions and is trapped in the polyimide film. Is the result. On the other hand, the diamine catalysts presented in the present invention showed characteristics that can be easily removed even at low temperatures without remaining due to the low boiling point as can be confirmed through Examples 1 to 3.

Claims (10)

Catalyst for imidation reaction represented by the following formula (1): [Formula 1]

In Chemical Formula 1, R ₁ , R ₂ , R ₃ , R <_4> , R <_5> and R <_6> represent a hydrogen atom, a C1-C12 alkyl group, or a C1-C12 hydroxy alkyl group, respectively, and n is an integer of 0-4. According to claim 1, wherein R ₁ , R ₂ , R ₃ And R ₄ are each an alkyl group having 1 to 12 carbon atoms, and R ₅ And R ₆ each represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a hydroxy alkyl group having 1 to 12 carbon atoms, and n is an integer of 0 to 4; According to claim 1, Formula 1 is N, N, N ', N' -tetramethylethylenediamine, N, N, N', N' -tetramethylpropylenediamine and N, N, N ', N'- A catalyst, characterized in that selected from tetramethylbutylenediamine. In the method of producing a polyimide resin by imidating a polyamic acid, Method for producing a polyimide resin, characterized in that using the diamine compound represented by the following formula (1) as the catalyst for the imidization reaction: [Formula 1]

In Formula 1, R ₁ , R ₂ , R _3, and R ₄ are each an alkyl group having 1 to 12 carbon atoms, and R ₅ and R ₆ each include a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a hydroxyl group. An alkyl group having 1 to 12 carbon atoms is represented, and n is an integer of 0 to 4; The method according to claim 4, wherein R ₁ , R ₂ , R ₃ And R ₄ are each an alkyl group having 1 to 12 carbon atoms, and R ₅ And R ₆ each represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a hydroxy alkyl group having 1 to 12 carbon atoms, and n is an integer of 0 to 4; The diamine compound according to claim 4, wherein the diamine compound is N, N, N ', N' -tetramethylethylenediamine, N, N, N', N' -tetramethylpropylenediamine and N, N, N ', N'- Method of producing a tetramethylbutylenediamine. The method of claim 4, wherein the diamine compound is used in the range of 0.1 to 200% by weight based on the polyamic acid. The method according to claim 4, wherein the imidization reaction is performed at a temperature in the range of 100 to 400 ° C. The method according to claim 4 or 8, wherein the imidization reaction is performed at a temperature in the range of 100 to 200 ° C. The production method according to claim 4, wherein the imidation reaction is in an imidization ratio of 95 to 100% and the amount of residual catalyst in the polyimide resin is 0 to 10% by weight.